CN110305579A - 耐磨耐刮及使用寿命长的不粘涂层及其涂覆方法 - Google Patents
耐磨耐刮及使用寿命长的不粘涂层及其涂覆方法 Download PDFInfo
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Abstract
本发明涉及一种不粘涂层,特别涉及耐磨耐刮及使用寿命长的不粘涂层及其涂覆方法。一种耐磨耐刮及使用寿命长的不粘涂层,包括底漆、中漆和面漆,所述的底漆是由含有聚醚砜或聚苯硫醚中的一种或两种与聚酰胺酰亚胺的底漆组合物涂覆得到,底漆组合物中聚醚砜与聚酰胺酰亚胺溶液的重量比为100:1‑20,PAI溶液的固体含量为20‑40%。本发明通过聚酰胺酰亚胺对聚醚砜进行混合改性,让聚醚砜进一步交联,聚酰胺酰亚胺在聚醚砜涂层内部形成一种网状支撑,提高涂层的耐热性能及在高温下对基材的附着力,同时提高聚醚砜在高温下面的机械强度。同时群岛状涂层结构,使得高点处涂层够厚,可以提供强有力的支撑,提高涂层的使用寿命。
Description
技术领域
本发明涉及一种不粘涂层,特别涉及耐磨耐刮及使用寿命长的不粘涂层及其涂覆方法,属于不粘涂层技术领域。
背景技术
聚四氟乙烯(PTFE)涂层需要依靠粘结剂才能很好地结合到基材,但目前的粘接剂聚醚砜(PES),聚苯硫醚(PPS)等都是热塑性树脂,在200℃以上耐温性能不高,由于在200℃以上高温下树脂会变软,跟基材的附着力下降,在这种环境下炊具在反复使用过程中会导致涂层起泡,脱落,尤其是在有使用锅铲等类似刮擦的情况下,情况更严重;聚酰胺酰亚胺(PAI)粘结剂是热固性树脂,耐温好,在高温下使用不会有脱落问题,但是不能厚涂,厚涂会起泡和开裂。由于氟涂层的致密性不高,涂层在使用过程中,水分子会渗透到底油,造成聚酰胺酰亚胺(PAI)会产生一定的水解,加上涂层自身的磨损,由于涂层膜厚不是很厚,整体涂层的使用寿命不长。目前行业中用聚酰胺酰亚胺(PAI)和聚醚砜(PES)共混作为底漆粘接剂的也很多,但都是以聚酰胺酰亚胺和聚醚砜为粘接剂,或者两者共混,加上一定的氟树脂作为底漆,然后喷涂中,面漆,底漆的膜厚一般不超过20微米,厚了会导致最终漆膜鼓泡,底油和中面油的结合力下降等问题,总体膜厚一般在50微米以下。
发明内容
本发明旨在针对现有的氟树脂涂层的上述缺陷,提供一种耐磨耐刮及使用寿命长的不粘涂层。
本发明还提供一种耐磨耐刮及使用寿命长的不粘涂层的涂覆方法。
本发明解决其技术问题所采用的技术方案是:
一种耐磨耐刮及使用寿命长的不粘涂层,包括底漆、中漆和面漆,所述的底漆是由含有聚醚砜(PES)或聚苯硫醚(PPS)中的一种或两种与聚酰胺酰亚胺(PAI)的底漆组合物涂覆得到,底漆组合物中聚醚砜(PES)与聚酰胺酰亚胺(PAI)溶液的重量比为100:1-20,PAI溶液的固体含量为20-40%。进一步优选的是,PAI以水溶液形式作为原料添加,PAI溶液的固体含量为28-33%。
中漆含聚醚砜、聚苯硫醚与聚酰胺酰亚胺中的一种或多种和四氟乙烯。面漆为含氟聚合物。底漆组合物是水性涂料或溶剂型涂料,优选水性涂料。
本发明的创新点是控制不粘涂层配方中聚酰胺酰亚胺(PAI)/聚苯硫醚(PPS)和聚醚砜(PES)的比例,结合底漆的溶剂体系,喷涂后以一种粉状的形态附着在基材上,再经过高温烧结,形成一种群岛状结构的底漆(常规底漆和本发明岛状结构底漆的截面示意图见图3),漆膜可以达到150微米。在使用过程中,凸起的部分形成坚韧耐磨的支撑,保护凹面的氟涂层不被刮伤,以提供整个涂层一个长期的使用寿命。
本发明的不粘涂层改善了现有以聚醚砜(PES),聚苯硫醚等为粘结剂的不粘涂层的耐温性和起泡脱落的问题,改善了以聚酰胺酰亚胺(PAI)为粘接剂及聚醚砜/聚苯硫醚与聚酰胺酰亚胺共混作为粘接剂的不粘涂层不能厚涂的问题,使得该涂层在耐磨,耐刮,使用寿命等方面的综合性能有很大提高。
作为优选,所述的底漆具有凹凸不平的岛状结构,其干膜厚度为40-150微米(直接测量值),优选80-120微米;中,面漆的总厚度为10-50微米。
作为优选,底漆组合物是由如下组分组成:聚醚砜或聚苯硫醚或二者混合物100%,以聚醚砜或聚苯硫醚或二者混合物的重量百分比计为100%计,还包括PAI1-20%,助剂0-3%,颜料0-3%,以及适量溶剂。
作为优选,所述的溶剂是由高沸点溶剂和低沸点溶剂组合而成,高沸点溶剂是甘油、甲基吡咯烷酮(NMP)或丙二醇中的一种或多种,低沸点溶剂是水、乙醇、异丙醇、甲苯或二甲苯中的一种或多种,高沸点溶剂和低沸点溶剂的重量比是25-35:100。进一步优选的是,所述的溶剂是由NMP、乙醇、甘油和水组成,NMP、乙醇、甘油和水的重量比为8-10:15-35:4.7-9:23.5-35。
作为优选,中漆组合物是由如下以重量百分比计的组分组成:
作为优选,面漆组合物是由如下以重量百分比计的组分组成:
本发明还提供一种特殊的施工方法,将基材预热到一定的温度,将底漆喷涂到基材上,控制配方中溶剂的挥发速率,让底漆在喷涂完之后以一种粉体的形状附着在基材上,以避免烘烤成膜过程中气泡的产生,再经过至少300℃以上的高温固化,形成岛状结构的涂层。
一种所述的耐磨耐刮及使用寿命长的不粘涂层的底漆涂覆方法,该涂覆方法包括如下步骤:将铝基材喷砂使其表面粗糙,用碱液和水清洗干净并预热到50-100℃,具体温度视基材大小和厚度而定;然后将混合得到的底漆材料喷涂在铝基材上,高温固化后形成岛状结构,烧结温度控制在380-420℃范围内,时间5-10分钟,底漆形成后自然冷却到室温。
作为优选,所述铝基材表面粗糙度为2-5微米。
一种所述的耐磨耐刮及使用寿命长的不粘涂层的涂覆方法,该涂覆方法包括如下步骤:将铝基材喷砂使其表面粗糙,用碱液和水清洗干净并预热到50-100℃,具体温度视基材大小和厚度而定;然后将混合得到的底漆材料喷涂在铝基材上,高温固化后形成岛状结构,烧结温度控制在380-420℃范围内,时间5-10分钟,底漆形成后自然冷却到室温;将中漆组合物喷涂在制得的底漆上,干燥温度100-180℃,时间5-10分钟,最后将面漆组合物喷涂在中漆上,经过380-420℃烧结5-10分钟,得到所述的不粘涂层。
与现有技术相比,本发明的特点体现在以下几点:
1.聚醚砜的耐腐蚀性能,耐水解和蒸汽性能,耐化学性能优异,但耐温性不强。聚酰胺酰亚胺耐温性好,但不能厚涂,并且耐水解性能不强,涂层使用寿命不长。本发明通过聚酰胺酰亚胺对聚醚砜进行混合改性,让聚醚砜进一步交联,聚酰胺酰亚胺在聚醚砜涂层内部形成一种网状支撑,提高涂层的耐热性能及在高温下对基材的附着力,同时提高聚醚砜在高温下面的机械强度。同时群岛状涂层结构,使得高点处涂层够厚,可以提供强有力的支撑,提高涂层的使用寿命。当聚醚砜含量过大时耐热性能会下降,当聚酰胺酰亚胺含量过大时涂层容易起泡,并且在烘烤过程中聚酰胺酰亚胺会与聚醚砜分离,不能均匀地混合在一起。
2.优选的聚醚砜粘接剂是羟端基的,使用分子量大的聚醚砜树脂粉末可以提高涂层的耐热性能。另外羟端基的聚醚砜可以提高跟基材的附着力,及高温熔融成膜过程中和聚酰胺酰亚胺之间的混合均匀稳定性。
3.在优选的实施方案中,将底漆中甲基吡咯烷酮(NMP)的含量提升,可以提高涂层与基材的附着力,甲基吡咯烷酮与聚醚砜的重量比为1:3到1:1,优选1:3。
4.在优选的实施方案中,高沸点溶剂的加入有助于不粘涂层的施工性,考虑安全性和环境友好型,甘油是优选的溶剂。
5.本发明中的底漆喷涂出来以粉状的形态附着在基材上。本发明底漆中的溶剂体系是高沸点溶剂和低沸点溶剂(高沸点溶剂是甘油、甲基吡咯烷酮,低沸点溶剂是水、乙醇,高沸点溶剂和低沸点溶剂的重量比是25-35:100)相结合,以利于底漆喷涂出来以粉状的形态附着在基材上。加入适量的挥发性溶剂可以提高涂层的施工性。
6.在施工底漆后,需要经过300℃以上的高温烧结一次,行成一种凹凸不平的岛状结构涂层,再施工中间层和面漆,或者直接施工面漆。中间层由含氟聚合物和聚醚砜,聚苯硫醚,聚酰胺酰亚胺其中的一种或多种构成,面层由含氟聚合物和少量粘接剂构成。
附图说明
图1是基材上涂覆的底漆照片,左常规底漆,右本发明岛状结构底漆;
图2是基材上涂覆的底漆80倍显微镜图,左常规底漆,右本发明岛状结构底漆;
图3是常规底漆和本发明岛状结构底漆的截面示意图。
具体实施方式
下面通过具体实施例,对本发明的技术方案作进一步的具体说明。应当理解,本发明的实施并不局限于下面的实施例,对本发明所做的任何形式上的变通和/或改变都将落入本发明保护范围。
在本发明中,若非特指,所有的份、百分比均为重量单位,所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法,如无特别说明,均为本领域的常规方法。
助剂,型号TX-100,陶氏化学;
聚醚砜(氯端基),熔融指数50-60,聚醚砜树脂,购自苏威(上海)有限公司;
聚醚砜(羟端基,熔融指数20-30),聚醚砜树脂,购自住友化学株式会社;
聚苯硫醚,购自深圳深日油墨有限公司;
聚酰胺酰亚胺,购自苏威(上海)有限公司。
测试方法
1.热硬度测试:
通过铅笔硬度对漆膜硬度进行评定。将漆膜加热到280度,用硬度不同的铅笔(中华牌),笔尖以45度角在涂层表面上前移,直至划破涂层,漏出基材,测试涂层的耐温性能。
2.附着力测试
a,用刀具在涂层上划1mm的小格100格,将沸腾的开水倒入内锅中浸泡30分钟
b,用纸巾擦净涂层的水和杂质,在同一45度对角位置用3M胶布粘紧涂层,然后以90度角快速拉起胶布,重复5次后不能有任何小格涂层脱落。
3.使用寿命测试:炒菜测试
测试条件:
a.煮番茄汤:加入醋,水,切片的西红柿,盐,加热并保持沸腾5min;
b.煎炒土豆片:加入植物油,升温后加入土豆片翻炒6min
c.煎炒排骨:加入植物油,升温后加入排骨翻炒4min,加入番茄酱及白糖翻炒8min;
d.炒螺蛳:加入植物油,升温后加入姜丝,螺蛳,料酒,豆瓣酱,辣椒酱等翻炒6min;
e.以a-d为一个模拟周期,每次烹饪结束后清洗锅具,观察涂层磨损情况,用电磁炉加热测试样锅至200+/-5℃,加入调配好的面粉;
f.持续加热至面饼上面变干,且出现轻微棕色,倾倒锅具,测试煎饼不粘性。
4.耐磨测试
测试条件:耐磨仪压力为3kg/21cm2,锅内加入适量5g/L洗洁精溶液,每250次更换百洁布。
5.耐刮测试
测试条件:A样品固定在耐刮伤性试验机(老虎爪试验机)的加热盘上面,水平安装圆珠笔芯;B加热样品锅至200+/-10℃,开启运行,并记录表面起皮,露基材的时间点。
实施例1-12
一种耐磨耐刮及使用寿命长的不粘涂层的底漆涂覆方法,具体是:将铝基材喷砂使其表面粗糙,粗糙度为2-5微米,然后用碱液和清水清洗干净并预热到50-100℃,具体温度视基材大小和厚度而定。本实施例采用基材厚度2mm,直径24cm的铝材,预热到80℃,然后将表1混合得到的底漆材料喷涂在铝基材上,高温固化后形成岛状结构,烧结温度控制在380-420℃范围内,时间5-10分钟,底漆形成后自然冷却到室温,得到的底漆性能数据见表2。
表1底漆配方(单位:kg)
注:PAI溶液的固体含量为30%。
表1(续)底漆配方(单位:kg)
注:PAI溶液的固体含量为30%。
表2
表2(续)
结论:熔融指数20-30的羟端基聚醚砜的附着力及漆膜热硬度比熔融指数50-60的氯端基的聚醚砜好。聚醚砜/聚酰胺酰亚胺的重量比超过100:20涂层容易起泡导致漆膜表面太粗糙。底漆中聚四氟乙烯的加入会降底热硬度。聚醚砜与聚酰胺酰亚胺的重量比为100:6条件下,较容易形成岛状结构,低沸点溶剂与高沸点溶剂的含量比例变化对施工性也有比较大的影响。在实施例1-3中,底漆漆膜成岛状结构的效果最好,漆膜凹凸有致,光滑,膜厚在70-100微米之间(膜厚指的是岛状结构顶部到底部高度,是膜厚计直接测量出来的数值)。图1是基材上涂覆的底漆照片,左常规底漆,右本发明岛状结构底漆;图2是基材上涂覆的底漆80倍显微镜图,左常规底漆,右本发明岛状结构底漆。由图1和图2可知,具有岛状结构的漆膜在使用过程中,由于凸起的顶部形成了强力的支撑,对凹面部分的氟表面产生了很好的保护,使得漆膜的持久不粘性和使用寿命得到很大的提升。
实施例13-21验证不同中漆配方对不粘涂层性能的影响
采用实施例2制得的不粘涂层的底漆,将表3的中漆喷涂在底漆上,干燥温度100-180℃,时间5-10分钟,最后将面漆喷涂在中漆上,经过380-420℃烧结5-10分钟,得到的不粘涂层的性能见表4。
表3中漆配方(单位:kg)
PAI溶液的固体含量为30%。
面漆配方(单位:kg)
表4性能比较
实施例 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 |
耐刮性(分钟) | 100 | 100 | 150 | 180 | 210 | 180 | 180 | 200 | 240 |
耐磨性(次) | 11000 | 11000 | 11000 | 12000 | 18000 | 18000 | 25000 | 27000 | 27000 |
炒菜测试(次) | 15 | 15 | 16 | 16 | 17 | 17 | 18 | 20 | 20 |
耐腐蚀(hr) | ≧96 | ≧96 | ≧96 | ≧96 | ≧96 | ≧96 | ≧96 | ≧96 | ≧96 |
结论:根据表2的数据可知,中漆中聚醚醚酮量的增加会增加涂层的耐磨和耐刮性能以及炒菜测试性能。
以上所述的实施例只是本发明的一种较佳的方案,并非对本发明作任何形式上的限制,在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
Claims (10)
1.一种耐磨耐刮及使用寿命长的不粘涂层,包括底漆、中漆和面漆,其特征在于:所述的底漆是由含有聚醚砜(PES)或聚苯硫醚(PPS)中的一种或两种与聚酰胺酰亚胺(PAI)的底漆组合物涂覆得到,底漆组合物中聚醚砜(PES)与聚酰胺酰亚胺(PAI)溶液的重量比为100:1-20,PAI溶液的固体含量为20-40%。
2.根据权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于:PAI以水溶液形式作为原料添加,PAI溶液的固体含量为28-33%。
3.根据权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于:所述的底漆具有凹凸不平的岛状结构,其干膜厚度为40-150微米;中,面漆的总厚度为10-50微米。
4.根据权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于底漆组合物是由如下组分组成:
聚醚砜或聚苯硫醚或二者混合物 100%,
以聚醚砜或聚苯硫醚或二者混合物的重量百分比计为100%计,还包括PAI 1-20%,助剂0-3%,颜料 0-3%,以及适量溶剂。
5.根据权利要求4所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于:所述的溶剂是由高沸点溶剂和低沸点溶剂组合而成,高沸点溶剂是甘油、甲基吡咯烷酮(NMP)或丙二醇中的一种或多种,低沸点溶剂是水、乙醇、异丙醇、甲苯或二甲苯中的一种或多种,高沸点溶剂和低沸点溶剂的重量比是25-35:100。
6.根据权利要求5所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于:所述的溶剂是由NMP、乙醇、甘油和水组成,NMP、乙醇、甘油和水的重量比为8-10:15-35:4.7-9:23.5-35。
7.根据权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于中漆组合物是由如下以重量百分比计的组分组成:
聚醚砜 0-5%
聚酰胺酰亚胺 5-10%
聚四氟乙烯 10-15%
聚醚醚酮 10-20%
甲基吡咯烷酮 10-15%
助剂 1-2 %
颜填料 6-12%
余量为水。
8.根据权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层,其特征在于面漆组合物是由如下以重量百分比计的组分组成:
聚四氟乙烯 40-44%
丙烯酸树脂 4-5%
珠光粉 2-3%
助剂 3-5%
三乙醇胺 4-6%
油酸 1-2%
晶须硅 2-4%
余量为水。
9.一种如权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层的底漆涂覆方法,其特征在于该涂覆方法包括如下步骤:将铝基材喷砂使其表面粗糙,用碱液和水清洗干净并预热到50-100℃,然后将混合得到的底漆材料喷涂在铝基材上,高温固化后形成岛状结构,烧结温度控制在380-420℃范围内,时间5-10分钟,底漆形成后自然冷却到室温。
10.一种如权利要求1所述的耐磨耐刮及使用寿命长的不粘涂层的涂覆方法,其特征在于该涂覆方法包括如下步骤:将铝基材喷砂使其表面粗糙,用碱液和水清洗干净并预热到50-100℃,然后将混合得到的底漆材料喷涂在铝基材上,高温固化后形成岛状结构,烧结温度控制在380-420℃范围内,时间5-10分钟,底漆形成后自然冷却到室温;将中漆组合物喷涂在制得的底漆上,干燥温度100-180℃,时间5-10分钟,最后将面漆组合物喷涂在中漆上,经过380-420℃烧结5-10分钟,得到所述的不粘涂层。
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